EP1591468B1 - Hot melt compounds made from copolyamides and crosslinkable copolyamide-block-polyethers - Google Patents

Hot melt compounds made from copolyamides and crosslinkable copolyamide-block-polyethers Download PDF

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Publication number
EP1591468B1
EP1591468B1 EP05290820.9A EP05290820A EP1591468B1 EP 1591468 B1 EP1591468 B1 EP 1591468B1 EP 05290820 A EP05290820 A EP 05290820A EP 1591468 B1 EP1591468 B1 EP 1591468B1
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Prior art keywords
acid
diamine
omega
alpha
polyamides
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German (de)
French (fr)
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EP1591468A1 (en
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Annett Linnemann
Thierry Briffaud
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Arkema France SA
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Arkema France SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/21—Paper; Textile fabrics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects
    • C08G2261/132—Morphological aspects branched or hyperbranched

Definitions

  • Hot melt adhesives are thermoplastic materials that are solid at room temperature and that, when heated (around 180 ° C), become more or less viscous liquids. These liquids are applied to a first substrate and then covered with a second surface. By cooling, adhesion is obtained between the substrate and the second surface.
  • the open time is the period during which the adhesive that has been applied to a substrate that is at room temperature remains sticky, that is to say the time interval during which the second surface can be applied and by cooling to obtain adhesion between the substrate and the second surface. After this time of open time it is no longer possible to obtain sufficient adhesion between the substrate and the second surface.
  • HMA hot melt adhesives
  • thermoadhesives in the textile field (fastening of woven and nonwoven fabrics), electronics (coating of copper wires for coils), or automobiles are applied at temperatures above their melting points and they adhere well to different surfaces.
  • the thermal resistance of thermoadhesives is therefore limited to their melting point, and often already at 10 ° C below their melting point, the product becomes soft and less adhesive.
  • an increase in the performance of thermoadhesives is required, such as better adhesion to treated surfaces, higher thermal strengths, or better resistance of the bonding to cleaning. steam or dry cleaning solvents. This performance improvement must be done without changing their application technology.
  • One way to improve the performance of an HMA is to crosslink it after gluing.
  • UV + micro waves, beta or gamma rays The unsaturated monoacids used as chain limiter allow the direct integration of the reactive principle in the polymer, which makes the product applicable without additional formulation.
  • thermoadhesives comprising these branched polyamides with unsaturated ends. They can be easily crosslinked either by heat using peroxides as initiator or by UV (or UV melting) using UV-sensitive initiators or by gamma or beta irradiation.
  • the invention also relates to the use of these branched polyamides with unsaturated ends as thermoadhesives.
  • the invention also relates to the use of these branched polyamides with unsaturated ends for sheathing electrical cables.
  • the multifunctional monomer (A) it is thus meant any product on which is a lactam, after the opening of its cycle, a diamine or a diacid can react and bind.
  • the functional monomers (A) are chosen from diethylenetriamine, mellitic acid, pentaerythritol and 2,2-dimethylolpropionic acid.
  • the proportion of (A) is between 0.05 and 5% by weight of all of (A) and the above monomers.
  • the proportion of (A) is between 0.05 and 2% by weight of the whole of (A) and the above monomers.
  • polyamide linkages mention may be made of the copolyamides resulting from the condensation of at least two alpha-omega-aminocarboxylic acids (not having the same number of carbon atoms) or of two lactams (not having the same number of carbon atoms). same number of carbon atoms) or a lactam and an alpha omega aminocarboxylic acid
  • copolyamides resulting from the condensation of at least one alpha omega acid aminocarboxylic acid (or a lactam), at least one diamine and at least one diacid dicarboxylic acid may also be mentioned.
  • copolyamides resulting from the condensation of either a lactam or an alpha-omega-aminocarboxylic acid or a diamine and a diacid may also be mentioned.
  • lactams include those having from 3 to 12 carbon atoms on the main ring and may be substituted. Examples that may be mentioned include ⁇ , ⁇ -dimethylpropiolactam, ⁇ , ⁇ -dimethylpropiolactam, amylolactam, caprolactam, capryllactam and lauryllactam.
  • alpha omega aminocarboxylic acid there may be mentioned amino-undecanoic acid and aminododecanoic acid.
  • a dicarboxylic acid mention may be made of adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, isophthalic acid, butanedioic acid and 1,4-cyclohexanedicarboxylic acid.
  • dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC - (CH 2 ) 10 -COOH.
  • the diamine may be an aliphatic diamine having 6 to 12 carbon atoms, it may be aryl and / or saturated cyclic.
  • IPD isophorone diamine
  • MPMD methyl pentamethylenediamine
  • MPMD bis (aminocyclohexyl) methane
  • BMACM bis (3-methyl-4-aminocyclohexyl
  • the copolyamide sequences comprise at least caprolactam and lauryllactam. According to another advantageous form, they comprise at least caprolactam, hexamethylenediamine and adipic acid.
  • copolyamide chains By way of examples of copolyamide chains, mention may be made of those of caprolactam and lauryl lactam (6/12), those of caprolactam and lauryl lactam and amino acid 11 undecanoic (6/11/12), those of caprolactam, adipic acid and hexamethylenediamine (6 / 6-6), caprolactam, lauryllactam, adipic acid and hexamethylenediamine (6/12 / 6-6), caprolactam, lauryllactam, of 11-amino-undecanoic acid, azelaic acid and hexamethylenediamine (6 / 6-9 / 11/12), caprolactam, lauryllactam, amino-11-undecanoic acid, adipic acid and hexamethylene diamine (6 / 6-6 / 11/12), those of lauryllactam, azelaic acid and hexamethylenediamine (PA 6-9 / 12).
  • unsaturated monoacid mention may be made, for example, of acrylic, methacrylic, cinnamic, crotonic, citraconic, itaconic, vinylacetic, undecylenic, maleic, fumaric, 5-norbornene-2 acrylic and 3-furan-2 acrylic acids, 3-pyrrole-2 acrylic, N-allyl aminobenzoic N-acryloyl aminobenzoic, N-methacryloyl aminobenzoic, acryloyloxybenzoic, methacryloyloxybenzoic, N-acryloyl or N-methacryloyl p-aminophenylacetic, N-allyl amino-11-undecanoic. It would not depart from the scope of the invention using a mixture of two or more of these acids. The salts and esters of these acids can also be used.
  • the multifunctional monomer (A) within the meaning of the present invention may be present during the condensation of the monomers of the polyamide or subsequently added and a catalyst may be added. It is recommended if the functions of the multifunctional monomer (A) are OH to add a catalyst. This catalyst can be added at the beginning of the reaction or after the condensation of the monomers of the polyamide linkages. This The catalyst may be the one used to condense polyamide blocks with carboxylic ends and diols such as, for example, polyethylene glycols or polytetramethylene glycols. These catalysts are used in the preparation of polyether block copolymers and polyamide blocks.
  • the catalyst is advantageously a derivative of a metal (M) chosen from the group formed by titanium, zirconium and hafnium.
  • tetraalkoxides which correspond to the general formula M (OR) 4 , in which M represents titanium, zirconium or hafnium, and R, which may be identical or different, denote alkyl radicals, linear or branched, having from 1 to 24 carbon atoms.
  • the C 1 to C 24 alkyl radicals from which the R radicals of the tetraalkoxides used as catalysts in the process according to the invention are chosen are, for example, methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl and hexadodecyl. .
  • the preferred catalysts are tetraalkoxides for which the radicals R, which may be identical or different, are C 1 to C 8 alkyl radicals.
  • the radicals R which may be identical or different, are C 1 to C 8 alkyl radicals.
  • examples of such catalysts are in particular Z r (OC 2 H 5 ) 4 , Z r (O-isoC 3 H 7 ) 4 , Z r (OC 4 H 9 ) 4 , Z r (OC 5 H 11 ) 4 , Z r (OC 6 H 13) 4, H f (OC 2 H 5) 4, H f (OC 4 H 9) 4, H f (O-ISOC 3 H 7) 4.
  • the catalyst used may consist solely of one or more of the tetraalkoxides of formula M (OR) 4 defined previously. It can also be formed by the combination of one or more of these tetraalkoxides with one or more alkali or alkaline-earth alkoxides of formula (R 1 O) p Y in which R 1 denotes a hydrocarbon residue, advantageously an alkyl residue in C 1 to C 24 , and preferably C 1 to C 8 , Y is an alkali or alkaline earth metal and p is the valence of Y.
  • the amounts of alkali or alkaline earth alkoxide and tetraalkoxides of zirconium or Hafnium that is associated to constitute the mixed catalyst can vary within wide limits. However, it is preferred to use amounts of alcoholate and tetraalkoxides such that the molar proportion of alkoxide is substantially equal to the molar proportion of tetraalkoxide.
  • the proportion by weight of catalyst that is to say of the tetraalkoxides or when the catalyst does not contain alkali or alkaline earth alkoxide or all of the tetraalkoxides and alkali or alkaline alcoholate or alkali when the catalyst is formed by the combination of these two types of compounds, preferably varies from 0.01 to 5% of the weight of the mixture of polyamide and multifunctional monomer (A), and is preferably between 0.05 and 0.05. and 2% of that weight.
  • salts of the metal (M) in particular the salts of (M) and of an organic acid and the complex salts between the oxide of (M) and / or (M) hydroxide and an organic acid.
  • the organic acid may be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauroyl acid, myristic, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and crotonic acid.
  • Acetic and propionic acids are particularly preferred.
  • M is zirconium.
  • These salts may be called zirconyl salts. Applicant without being bound by this explanation think that these salts of zirconium and an organic acid or complex salts mentioned above release ZrO ++ during the process.
  • the product sold under the name of zirconyl acetate is used. The quantity to be used is the same as for the M (OR) 4 derivatives.
  • the average molar mass by weight mw is between 10,000 and 30,000 g / mol.
  • MFI (short for Flow Index or Index) melt flow rate) can be between 5 and 35 g / 10 min (130 ° C, 2.16 kg)
  • crosslinking With regard to crosslinking the advantage of the products of the present invention is that they are used as conventional thermoadhesives with the same machines. After gluing the materials, the crosslinking is carried out.
  • the heat source may be infrared radiation, the crosslinking is between 30 seconds and 5 minutes. If it is crosslinked under UV or UV and microwave, the crosslinking is between 15 and 30 seconds. As for the crosslinking under gamma or beta radiation crosslinking is done in less than one second.
  • UV crosslinking makes it possible to separate the application period of the melt product from the crosslinking period, although the crosslinking is more effective in combination with a warming of the product, such as by microwaves.
  • the advantage of using beta or gamma rays to crosslink is that it is almost instantaneous and no initiator is needed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polyamides (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Organic Insulating Materials (AREA)
  • Paints Or Removers (AREA)

Description

Domaine de l'inventionField of the invention

La présente invention concerne des polyamides branchés à extrémités insaturées. Ils peuvent être fabriqués par copolymérisation des monomères usuels formant les polyamides (lactames, acides alpha-oméga-aminocarboxyliques, diacides et diamines) en présence d'un monomère multifonctionnel (A) ayant plus de 2 fonctions et en utilisant un monoacide insaturé comme limiteur de chaîne. Le monomère multifonctionnel

  1. (A) utilisé dans le cadre de l'invention est choisi parmi la diéthylenetriamine, l'acide mellitique, le pentaérythritol et le 2,2 diméthyloopropionique acide. Ces polyamides branchés à extrémités insaturées sont réticulables. Ils peuvent être réticulés facilement soit par la chaleur en utilisant des peroxydes comme initiateur soit par rayonnement UV (ou fusion sous UV) en utilisant des initiateurs sensibles aux UV soit par irradiation par des rayons gamma ou bêta. On peut les utiliser comme adhésifs réticulables ou pour le gainage de câbles électriques et en général pour obtenir des objets ayant des propriétés mécaniques et une tenue en température améliorées.
The present invention relates to branched polyamides with unsaturated ends. They can be manufactured by copolymerization of the usual monomers forming the polyamides (lactams, alpha-omega-aminocarboxylic acids, diacids and diamines) in the presence of a multifunctional monomer (A) having more than 2 functions and using an unsaturated monoacid as a reducing agent. chain. Multifunctional monomer
  1. (A) used in the context of the invention is selected from diethylenetriamine, mellitic acid, pentaerythritol and 2,2-dimethylooprionic acid. These branched polyamides with unsaturated ends are crosslinkable. They can be easily crosslinked either by heat using peroxides as initiator or by UV (or UV melting) using UV-sensitive initiators or by gamma or beta irradiation. They can be used as crosslinkable adhesives or for sheathing electric cables and generally to obtain objects having improved mechanical properties and temperature resistance.

L'art antérieur et le problème techniqueThe prior art and the technical problem

Les colles (adhésifs) thermofusibles sont des matériaux thermoplastiques solides à la température ambiante et qui par chauffage (environ vers 180°C) deviennent des liquides plus ou moins visqueux. Ces liquides sont appliqués sur un premier substrat puis on le couvre avec une seconde surface. Par refroidissement, on obtient une adhérence entre le substrat et la deuxième surface. Le temps ouvert est la période pendant laquelle la colle qui a été appliquée sur un substrat qui est à la température ambiante reste collante, c'est-à-dire l'intervalle de temps pendant lequel on peut appliquer la seconde surface et par refroidissement obtenir une adhérence entre le substrat et la seconde surface. Passé ce délai du temps ouvert on ne peut plus obtenir une adhérence suffisante entre le substrat et la seconde surface. Ces colles peuvent aussi être disposées à l'état solide entre les deux matériaux à coller puis on chauffe l'ensemble, la colle fond et par refroidissement les deux matériaux sont collés l'un sur l'autre. Cette technique est utilisée dans l'industrie textile, la colle est sous forme de film ou de poudre qu'on dispose entre deux tissus puis à l'aide d'un fer chaud on provoque le collage. Ces colles sont désignées par l'abréviation HMA (hot melt adhesives) et sont parfois aussi désignées par le mot "thermoadhésifs".Hot melt adhesives are thermoplastic materials that are solid at room temperature and that, when heated (around 180 ° C), become more or less viscous liquids. These liquids are applied to a first substrate and then covered with a second surface. By cooling, adhesion is obtained between the substrate and the second surface. The open time is the period during which the adhesive that has been applied to a substrate that is at room temperature remains sticky, that is to say the time interval during which the second surface can be applied and by cooling to obtain adhesion between the substrate and the second surface. After this time of open time it is no longer possible to obtain sufficient adhesion between the substrate and the second surface. These glues can also be arranged in the solid state between the two materials to be glued, then the whole is heated, the glue melts and cooling the two materials are glued to one another. This technique is used in the textile industry, the glue is in the form of film or powder that is available between two fabrics and then using a hot iron it causes the bonding. These glues are designated by the abbreviation HMA (hot melt adhesives) and are sometimes also referred to as "thermoadhesives".

Les polyamides classiquement utilisés comme thermoadhésifs dans le domaine textile (fixation des tissés et non-tissés), électronique (enrobage des fils de cuivre pour bobines ), ou automobile sont appliqués à des températures supérieures à leurs points de fusion et ils adhérent bien sur différentes surfaces. La tenue thermique des thermoadhésifs est donc limitée à leur point de fusion, et souvent déjà à 10°C en dessous de leur point de fusion, le produit devient mou et moins adhésif. Aujourd'hui on observe dans tous les domaines d'application qu'une augmentation de la performance des thermoadhésifs est demandée, comme par exemple une meilleure adhésion sur des surfaces traitées, des tenues thermiques plus élevées, ou une meilleure résistance du collage au nettoyage à la vapeur ou aux solvants de nettoyage à sec. Cette amélioration des performances doit se faire sans changer leur technologie d'application. Un moyen d'améliorer les performances d'un HMA est de le réticuler après le collage.The polyamides conventionally used as thermoadhesives in the textile field (fastening of woven and nonwoven fabrics), electronics (coating of copper wires for coils), or automobiles are applied at temperatures above their melting points and they adhere well to different surfaces. The thermal resistance of thermoadhesives is therefore limited to their melting point, and often already at 10 ° C below their melting point, the product becomes soft and less adhesive. Today it is observed in all areas of application that an increase in the performance of thermoadhesives is required, such as better adhesion to treated surfaces, higher thermal strengths, or better resistance of the bonding to cleaning. steam or dry cleaning solvents. This performance improvement must be done without changing their application technology. One way to improve the performance of an HMA is to crosslink it after gluing.

L'art antérieur a déjà décrit la réticulation des polyamides et des copolyamides. Les brevets DE 3725486 , EP 940461 , WO2002026887 décrivent une réticulation par des isocyanates. Les brevets WO2002086009 , US6515048 décrivent une réticulation par des époxy. Le brevet EP326444 décrit une réticulation par un agent préalablement encapsulé. Le brevet US6111030 décrit des polyamides à terminaisons amine pour réticuler des époxy, des polysulfures ou des cyanoacrylates. L'inconvénient de ces systèmes est l'utilisation nécessaire d'un coréactif qui peut être toxique comme les isocyanates, les acrylates, ou les résines époxydes. On a maintenant trouvé des copolyamides branchés à extrémités insaturées. La réaction de réticulation s'effectue par des groupements insaturés qui sont faciles à activer par irradiation (chaleur, UV,The prior art has already described the crosslinking of polyamides and copolyamides. Licences DE 3725486 , EP 940461 , WO2002026887 describe cross-linking with isocyanates. Licences WO2002086009 , US6515048 describe crosslinking by epoxies. The patent EP326444 describes a crosslinking by a previously encapsulated agent. The patent US6111030 describes amine-terminated polyamides for cross-linking epoxies, polysulfides or cyanoacrylates. The disadvantage of these systems is the necessary use of a coreactant which may be toxic such as isocyanates, acrylates, or epoxy resins. We have now found branched copolyamides with unsaturated ends. The crosslinking reaction is carried out by unsaturated groups which are easy to activate by irradiation (heat, UV,

UV+ micro ondes, rayons bêta ou gamma). Les monoacides insaturés utilisés comme limiteur de chaine permettent l'intégration directe du principe réactif dans le polymère, ce qui rend le produit applicable sans formulation supplémentaire.UV + micro waves, beta or gamma rays). The unsaturated monoacids used as chain limiter allow the direct integration of the reactive principle in the polymer, which makes the product applicable without additional formulation.

L'art antérieur a déjà décrit des polyamides à extrémités insaturées. Le brevet US6680264 décrit des polyamides hydrodispersibles à extrémités insaturées, ces produits ne sont pas des HMA. Les brevets EP147267 et WO2003087193 décrivent des polyamides linéaires à extrémités insaturées.The prior art has already described polyamides with unsaturated ends. The patent US6680264 describes water-dispersible polyamides with unsaturated ends, these products are not HMAs. Licences EP147267 and WO2003087193 describe linear polyamides with unsaturated ends.

L'avantage d'avoir plus de 2 extrémités insaturées est que la réaction de réticulation conduit à la formation d'un réseau tridimensionnel, par rapport à un simple allongement des chaînes. La réticulation est donc beaucoup plus rapide et plus efficace.The advantage of having more than 2 unsaturated ends is that the crosslinking reaction leads to the formation of a three-dimensional network, compared to a simple chain extension. Crosslinking is therefore much faster and more efficient.

Brève description de l'inventionBrief description of the invention

La présente invention concerne des polyamides branchés à extrémités insaturées comprenant:

  • au moins un motif provenant d'un monomère multifonctionnel (A) choisi parmi la diéthylène triamine, le pentaérythritol, l'acide mellitique et le 2,2-diméthylolpropionique acid,
  • au moins des enchaînements résultant de la condensation en présence d'au moins un monoacide insaturé utilisé comme limiteur de chaîne,
    • soit d'au moins deux acides alpha,omega-aminocarboxyliques n'ayant pas le même nombre d'atomes de carbone,
      • ➢ soit d'au moins deux lactames n'ayant pas le même nombre d'atomes de carbone,
      • > soit d'au moins un lactame, au moins un diacide carboxylique et au moins une diamine,
      • ➢ soit d'un lactame et/ou d'un acide alpha,omega-aminocarboxylique n'ayant pas le même nombre d'atomes de carbone,
      • ➢ soit d'une diamine et d'un diacide,
    • soit d'au moins une diamine, d'au moins un diacide carboxylique et d'au moins un acide alpha,omega-aminocarboxylique,
la proportion de (A) étant inférieure à 9% en poids de l'ensemble de (A) et des monomères ci dessus.The present invention relates to branched polyamides with unsaturated ends comprising:
  • at least one unit derived from a multifunctional monomer (A) selected from diethylene triamine, pentaerythritol, mellitic acid and 2,2-dimethylolpropionic acid,
  • at least sequences resulting from the condensation in the presence of at least one unsaturated monoacid used as a chain limiter,
    • at least two alpha, omega-aminocarboxylic acids that do not have the same number of carbon atoms,
      • ➢ at least two lactams that do not have the same number of carbon atoms,
      • at least one lactam, at least one dicarboxylic acid and at least one diamine,
      • Or a lactam and / or an alpha, omega-aminocarboxylic acid which does not have the same number of carbon atoms,
      • ➢ is a diamine and a diacid,
    • at least one diamine, at least one dicarboxylic acid and at least one alpha, omega-aminocarboxylic acid,
the proportion of (A) being less than 9% by weight of all of (A) and the above monomers.

Ils peuvent être fabriqués par condensation en présence d'un monoacide insaturé comme limiteur de chaîne, d'au moins un monomère multifonctionnel (A) choisi parmi la diéthylène triamine, le pentaérythritol, l'acide mellitique et le 2,2-diméthylolpropionique acide, avec - soit d'au moins deux acides alpha,omega-aminocarboxyliques n'ayant pas le même nombre d'atomes de carbone,

  • ➢ soit d'au moins deux lactames n'ayant pas le même nombre d'atomes de carbone,
  • ➢ soit d'au moins un lactame, au moins un diacide carboxylique et au moins une diamine,
  • ➢ soit d'un lactame et/ou d'un acide alpha,omega-aminocarboxylique n'ayant pas le même nombre d'atomes de carbone,
  • ➢ soit d'une diamine et d'un diacide,
le monomère multifonctionnel (A) pouvant être présent pendant la condensation des monomères des enchaînements polyamide ou ajouté ensuite et un catalyseur pouvant être ajouté, la proportion de (A) étant inférieure à 9% en poids de l'ensemble de (A) et des monomères ci-dessus.They can be manufactured by condensation in the presence of a monoacid unsaturated chain limiter of at least one multifunctional monomer (A) selected from diethylene triamine, pentaerythritol, mellitic acid and 2,2-dimethylolpropionic acid, with - at least two alpha, omega acids aminocarboxylic acids not having the same number of carbon atoms,
  • ➢ at least two lactams that do not have the same number of carbon atoms,
  • At least one lactam, at least one dicarboxylic acid and at least one diamine,
  • Or a lactam and / or an alpha, omega-aminocarboxylic acid which does not have the same number of carbon atoms,
  • ➢ is a diamine and a diacid,
the multifunctional monomer (A) may be present during the condensation of the monomers of the polyamide linkages or subsequently added and a catalyst which can be added, the proportion of (A) being less than 9% by weight of the whole of (A) and the monomers above.

L'invention concerne aussi des thermoadhésifs comprenant ces polyamides branchés à extrémités insaturées. Ils peuvent être réticulés facilement soit par la chaleur en utilisant des peroxydes comme initiateur soit par rayonnement UV (ou fusion sous UV) en utilisant des initiateurs sensibles aux UV soit par irradiation par des rayons gamma ou bêta.The invention also relates to thermoadhesives comprising these branched polyamides with unsaturated ends. They can be easily crosslinked either by heat using peroxides as initiator or by UV (or UV melting) using UV-sensitive initiators or by gamma or beta irradiation.

L'invention concerne aussi l'utilisation de ces polyamides branchés à extrémités insaturées comme thermoadhésifs.The invention also relates to the use of these branched polyamides with unsaturated ends as thermoadhesives.

L'invention concerne aussi l'utilisation de ces polyamides branchés à extrémités insaturées pour gainer des câbles électriques.The invention also relates to the use of these branched polyamides with unsaturated ends for sheathing electrical cables.

Description détaillée de l'inventionDetailed description of the invention

S'agissant du monomère multifonctionnel (A), on désigne ainsi tout produit sur lequel soit un lactame, après l'ouverture de son cycle, soit une diamine, soit un diacide peut réagir et se fixer. Les monomères fonctionnels (A) sont choisis parmi la diéthylenetriamine, l'acide mellitique, le pentaérythritol et le 2,2-diméthylolpropionique acide. Avantageusement la proportion de (A) est comprise entre 0,05 et 5% en poids de l'ensemble de (A) et des monomères ci-dessus. De préférence la proportion de (A) est comprise entre 0,05 et 2% en poids de l'ensemble de (A) et des monomères ci dessus. As regards the multifunctional monomer (A), it is thus meant any product on which is a lactam, after the opening of its cycle, a diamine or a diacid can react and bind. The functional monomers (A) are chosen from diethylenetriamine, mellitic acid, pentaerythritol and 2,2-dimethylolpropionic acid. Advantageously, the proportion of (A) is between 0.05 and 5% by weight of all of (A) and the above monomers. Preferably the proportion of (A) is between 0.05 and 2% by weight of the whole of (A) and the above monomers.

S'agissant des enchaînements polyamides on peut citer les copolyamides résultant de la condensation d'au moins deux acides alpha-oméga-aminocarboxyliques (n'ayant pas le même nombre d'atomes de carbone) ou de deux lactames (n'ayant pas le même nombre d'atomes de carbone) ou d'un lactame et d'un acide alpha oméga aminocarboxylique As regards the polyamide linkages, mention may be made of the copolyamides resulting from the condensation of at least two alpha-omega-aminocarboxylic acids (not having the same number of carbon atoms) or of two lactams (not having the same number of carbon atoms). same number of carbon atoms) or a lactam and an alpha omega aminocarboxylic acid

(n'ayant pas le même nombre d'atomes de carbone). On peut encore citer les copolyamides résultant de la condensation d'au moins un acide alpha oméga aminocarboxylique (ou un lactame), au moins une diamine et au moins un diacide dicarboxylique. On peut encore citer les polyamides résultant de la condensation soit d'un lactame ou d'un acide alpha-oméga-aminocarboxylique soit d'une diamine et d'un diacide.(not having the same number of carbon atoms). It may also be mentioned copolyamides resulting from the condensation of at least one alpha omega acid aminocarboxylic acid (or a lactam), at least one diamine and at least one diacid dicarboxylic acid. Mention may also be made of polyamides resulting from the condensation of either a lactam or an alpha-omega-aminocarboxylic acid or a diamine and a diacid.

A titre d'exemple de lactames on peut citer ceux ayant de 3 à 12 atomes de carbone sur le cycle principal et pouvant être substitués. On peut citer par exemple le β,β-diméthylpropiolactame, le α,α-diméthylpropiolactame, l'amylolactame, le caprolactame, le capryllactame et le lauryllactame.Examples of lactams include those having from 3 to 12 carbon atoms on the main ring and may be substituted. Examples that may be mentioned include β, β-dimethylpropiolactam, α, α-dimethylpropiolactam, amylolactam, caprolactam, capryllactam and lauryllactam.

A titre d'exemple d'acide alpha oméga aminocarboxylique on peut citer l'acide amino-undécanoïque et l'acide aminododécanoïque. A titre d'exemple d'acide dicarboxylique on peut citer l'acide adipique, l'acide sébacique, l'acide dodécanedioïque, l'acide tetradécanedioïque, l'acide isophtalique, l'acide butanedioïque, l'acide 1,4 cyclohexanedicarboxylique, l'acide téréphtalique, le sel de sodium ou de lithium de l'acide sulphoisophtalique, les acides gras dimérisés (ces acides gras dimérisés ont une teneur en dimère d'au moins 98% et sont de préférence hydrogénés) et l'acide dodécanedioïque HOOC-(CH2)10-COOH.As an example of alpha omega aminocarboxylic acid there may be mentioned amino-undecanoic acid and aminododecanoic acid. By way of example of a dicarboxylic acid, mention may be made of adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, isophthalic acid, butanedioic acid and 1,4-cyclohexanedicarboxylic acid. terephthalic acid, sodium or lithium salt of sulphoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC - (CH 2 ) 10 -COOH.

La diamine peut être une diamine aliphatique ayant de 6 à 12 atomes de carbone, elle peut être arylique et/ou cyclique saturée. A titre d'exemples, on peut citer l'hexaméthylènediamine, la pipérazine, la tetraméthylène diamine, l'octaméthylène diamine, la décaméthylène diamine, la dodécaméthylène diamine, le 1,5 diaminohexane, le 2,2,4-triméthyl-1,6-diamino-hexane, les polyols diamine, l'isophorone diamine (IPD), le méthyl pentaméthylènediamine (MPMD), la bis(aminocyclohéxyl) méthane (BACM), la bis(3-méthyl-4 aminocyclohéxyl) méthane (BMACM).The diamine may be an aliphatic diamine having 6 to 12 carbon atoms, it may be aryl and / or saturated cyclic. By way of examples, mention may be made of hexamethylenediamine, piperazine, tetramethylenediamine, octamethylene diamine, decamethylene diamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1, 6-diamino-hexane, diamine polyols, isophorone diamine (IPD), methyl pentamethylenediamine (MPMD), bis (aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM).

Avantageusement, les enchaînements copolyamides comprennent au moins du caprolactame et du lauryllactame. Selon une autre forme avantageuse, ils comprennent au moins du caprolactame, de l'hexaméthylène diamine et de l'acide adipique.Advantageously, the copolyamide sequences comprise at least caprolactam and lauryllactam. According to another advantageous form, they comprise at least caprolactam, hexamethylenediamine and adipic acid.

A titre d'exemples d'enchainements copolyamides, on peut citer ceux de caprolactame et de lauryl lactame (6/12), ceux de caprolactame, de lauryl lactame et d'acide amino 11 undécanoïque (6/11/12), ceux de caprolactame, d'acide adipique et d'hexaméthylène diamine (6/6-6), ceux de caprolactame, de lauryllactame, d'acide adipique et d'hexaméthylène diamine (6/12/6-6), ceux de caprolactame, de lauryllactame, d'acide amino 11 undécanoïque, d'acide azélaïque et d'hexaméthylène diamine (6/6-9/11/12), ceux de caprolactame, de lauryllactame, d'acide amino 11 undécanoïque, d'acide adipique et d'hexaméthylène diamine (6/6-6/11/12), ceux de lauryllactame, d'acide azélaïque et d'hexaméthylène diamine (PA 6-9/12).By way of examples of copolyamide chains, mention may be made of those of caprolactam and lauryl lactam (6/12), those of caprolactam and lauryl lactam and amino acid 11 undecanoic (6/11/12), those of caprolactam, adipic acid and hexamethylenediamine (6 / 6-6), caprolactam, lauryllactam, adipic acid and hexamethylenediamine (6/12 / 6-6), caprolactam, lauryllactam, of 11-amino-undecanoic acid, azelaic acid and hexamethylenediamine (6 / 6-9 / 11/12), caprolactam, lauryllactam, amino-11-undecanoic acid, adipic acid and hexamethylene diamine (6 / 6-6 / 11/12), those of lauryllactam, azelaic acid and hexamethylenediamine (PA 6-9 / 12).

S'agissant du monoacide insaturé on peut citer à titre d'exemple les acides acrylique, méthacrylique, cinnamique, crotonique, citraconique, itaconique, vinylacétique, undécylénique, maléique, fumarique, 5-norbornène-2 acrylique, 3-furan-2 acrylique, 3-pyrrole-2 acrylique, N-allyl aminobenzoïque N-acryloyl aminobenzoïque, N-méthacryloyl aminobenzoïque, acryloyloxybenzoïque, méthacryloyloxybenzoïque, N-acryloyl ou N-méthacryloyl p- aminophénylacétique, N-allyl amino-11-undécanoïque. On ne sortirait pas du cadre de l'invention en utilisant un mélange de deux ou plusieurs de ces acides. On peut aussi utiliser les sels et les esters de ces acides. As regards the unsaturated monoacid, mention may be made, for example, of acrylic, methacrylic, cinnamic, crotonic, citraconic, itaconic, vinylacetic, undecylenic, maleic, fumaric, 5-norbornene-2 acrylic and 3-furan-2 acrylic acids, 3-pyrrole-2 acrylic, N-allyl aminobenzoic N-acryloyl aminobenzoic, N-methacryloyl aminobenzoic, acryloyloxybenzoic, methacryloyloxybenzoic, N-acryloyl or N-methacryloyl p-aminophenylacetic, N-allyl amino-11-undecanoic. It would not depart from the scope of the invention using a mixture of two or more of these acids. The salts and esters of these acids can also be used.

S'agissant du procédé de synthèse de ces copolyamides c'est la technique habituelle de synthèse des polyamides ou copolyamides pourvu qu'on effectue la condensation des monomères des enchaînements polyamide en présence d'un monoacide insaturé comme limiteur de chaîne. Selon une forme avantageuse, il est recommandé d'ajouter une diamine en excès pour assurer la fixation de la totalité d'acide insaturé sur le polymère, et pour favoriser une addition de type Michael (addition d'amine sur double liaison) comme réaction de réticulation. Regarding the process for synthesizing these copolyamides, it is the usual technique for synthesizing polyamides or copolyamides provided that the monomers of the polyamide linkages are condensed in the presence of an unsaturated monoacid as a chain limiter. According to an advantageous form, it is recommended to add an excess diamine to ensure the fixing of all the unsaturated acid on the polymer, and to promote a Michael-type addition (amine addition on a double bond) as a reaction of crosslinking.

Le monomère multifonctionnel (A) au sens de la présente invention peut être présent pendant la condensation des monomères des enchaînements polyamide ou ajouté ensuite et un catalyseur peut être ajouté. Il est recommandé si les fonctions du monomère multifonctionnel (A) sont des OH d'ajouter un catalyseur. Ce catalyseur peut être ajouté en début de réaction ou après la condensation des monomères des enchaînements polyamide. Ce catalyseur peut être celui qu'on utilise pour condenser des blocs polyamides à extrémités carboxyliques et des diols tels que par exemple des polyéthylène glycols ou des polytetraméthylene glycols. Ces catalyseurs sont utilisés dans la préparation des copolymères à blocs polyéthers et blocs polyamides.The multifunctional monomer (A) within the meaning of the present invention may be present during the condensation of the monomers of the polyamide or subsequently added and a catalyst may be added. It is recommended if the functions of the multifunctional monomer (A) are OH to add a catalyst. This catalyst can be added at the beginning of the reaction or after the condensation of the monomers of the polyamide linkages. This The catalyst may be the one used to condense polyamide blocks with carboxylic ends and diols such as, for example, polyethylene glycols or polytetramethylene glycols. These catalysts are used in the preparation of polyether block copolymers and polyamide blocks.

Le catalyseur est avantageusement un dérivé d'un métal (M) choisi dans le groupe formé par le titane, le zirconium et l' hafnium.The catalyst is advantageously a derivative of a metal (M) chosen from the group formed by titanium, zirconium and hafnium.

A titre d'exemple de dérivé on peut citer les tétraalcoxydes qui répondent à la formule générale M(OR)4, dans laquelle M représente le titane, le zirconium ou l'hafnium et les R, identiques ou différents, désignent des radicaux alcoyles, linéaires ou ramifiés, ayant de 1 à 24 atomes de carbone.
Les radicaux alcoyles en C1 à C24 parmi lesquels sont choisis les radicaux R des tétraalcoxydes utilisés comme catalyseurs dans le procédé suivant l'invention sont par exemple tels que méthyle, éthyle, propyl, isopropyl, butyle, éthylhexyl, décyl, dodécyl, hexadodécyl. Les catalyseurs préférés sont les tétraalcoxydes pour lesquels les radicaux R, identiques ou différents, sont des radicaux alcoyles en C1 à C8. Des exemples de tels catalyseurs sont notamment Zr (OC2H5)4, Zr (O-isoC3H7)4, Zr(OC4H9)4, Zr(OC5H11)4, Zr(OC6H13)4, Hf(OC2H5)4, Hf(OC4H9)4, Hf(O-isoC3H7)4.By way of example of a derivative, mention may be made of tetraalkoxides which correspond to the general formula M (OR) 4 , in which M represents titanium, zirconium or hafnium, and R, which may be identical or different, denote alkyl radicals, linear or branched, having from 1 to 24 carbon atoms.
The C 1 to C 24 alkyl radicals from which the R radicals of the tetraalkoxides used as catalysts in the process according to the invention are chosen are, for example, methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl and hexadodecyl. . The preferred catalysts are tetraalkoxides for which the radicals R, which may be identical or different, are C 1 to C 8 alkyl radicals. Examples of such catalysts are in particular Z r (OC 2 H 5 ) 4 , Z r (O-isoC 3 H 7 ) 4 , Z r (OC 4 H 9 ) 4 , Z r (OC 5 H 11 ) 4 , Z r (OC 6 H 13) 4, H f (OC 2 H 5) 4, H f (OC 4 H 9) 4, H f (O-ISOC 3 H 7) 4.

Le catalyseur utilisé peut consister uniquement en un ou plusieurs des tétraalcoxydes de formule M(OR)4 définis précédemment. Il peut encore être formé par l'association d'un ou plusieurs de ces tétraalcoxydes avec un ou plusieurs alcoolates alcalins ou alcalino-terreux de formule (R1O)pY dans laquelle R1 désigne un reste hydrocarboné, avantageusement un reste alcoyle en C1 à C24, et de préférence en C1 à C8, Y représente un métal alcalin ou alcalino-terreux et p est la valence de Y. Les quantités d'alcoolate alcalin ou alcalino-terreux et de tétraalcoxydes de zirconium ou d'hafnium que l'on associe pour constituer le catalyseur mixte peuvent varier dans de larges limites. On préfère toutefois utiliser des quantités d'alcoolate et de tétraalcoxydes telles que la proportion molaire d'alcoolate soit sensiblement égale à la proportion molaire de tétraalcoxyde.The catalyst used may consist solely of one or more of the tetraalkoxides of formula M (OR) 4 defined previously. It can also be formed by the combination of one or more of these tetraalkoxides with one or more alkali or alkaline-earth alkoxides of formula (R 1 O) p Y in which R 1 denotes a hydrocarbon residue, advantageously an alkyl residue in C 1 to C 24 , and preferably C 1 to C 8 , Y is an alkali or alkaline earth metal and p is the valence of Y. The amounts of alkali or alkaline earth alkoxide and tetraalkoxides of zirconium or Hafnium that is associated to constitute the mixed catalyst can vary within wide limits. However, it is preferred to use amounts of alcoholate and tetraalkoxides such that the molar proportion of alkoxide is substantially equal to the molar proportion of tetraalkoxide.

La proportion pondérale de catalyseur, c'est-à-dire du ou des tétraalcoxydes lorsque le catalyseur ne renferme pas d'alcoolate alcalin ou alcalino-terreux ou bien de l'ensemble du ou des tétraalcoxydes et du ou des alcoolates alcalins ou alcalino-terreux lorsque le catalyseur est formé par l'association de ces deux types de composés, varie avantageusement de 0,01 à 5 % du poids du mélange des enchaînements polyamide et du monomère multifonctionnel (A), et se situe de préférence entre 0,05 et 2 % de ce poids.The proportion by weight of catalyst, that is to say of the tetraalkoxides or when the catalyst does not contain alkali or alkaline earth alkoxide or all of the tetraalkoxides and alkali or alkaline alcoholate or alkali when the catalyst is formed by the combination of these two types of compounds, preferably varies from 0.01 to 5% of the weight of the mixture of polyamide and multifunctional monomer (A), and is preferably between 0.05 and 0.05. and 2% of that weight.

A titre d'exemple d'autres dérivés, on peut citer aussi les sels du métal (M) en particulier les sels de (M) et d'un acide organique et les sels complexes entre l'oxyde de (M) et/ou l'hydroxyde de (M) et un acide organique. Avantageusement l'acide organique peut être l'acide formique, l'acide acétique, l'acide propionique, l'acide butyrique, l'acide valérique, l'acide caproïque, l'acide caprylique, l'acide lauryque, l'acide myristique, l'acide palmitique, l'acide stéarique, l'acide oléique, l'acide linoléique, l'acide linolénique, l'acide cyclohexane carboxylique, l'acide phénylacétique, l'acide benzoïque, l'acide salicylique, l'acide oxalique, l'acide malonique, l'acide succinique, l'acide glutarique, l'acide adipique, l'acide maléique, l'acide fumarique, l'acide phtalique et l'acide crotonique. Les acides acétique et propionique sont particulièrement préférés. Avantageusement M est le zirconium. Ces sels peuvent s'appeler sels de zirconyle. La demanderesse sans être liée par cette explication pense que ces sels de zirconium et d'un acide organique ou les sels complexes cités plus haut libèrent ZrO++ au cours du procédé. On utilise le produit vendu sous le nom d'acétate de zirconyle. La quantité à utiliser est la même que pour les dérivés M(OR)4.By way of example of other derivatives, mention may also be made of the salts of the metal (M), in particular the salts of (M) and of an organic acid and the complex salts between the oxide of (M) and / or (M) hydroxide and an organic acid. Advantageously, the organic acid may be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauroyl acid, myristic, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and crotonic acid. Acetic and propionic acids are particularly preferred. Advantageously M is zirconium. These salts may be called zirconyl salts. Applicant without being bound by this explanation think that these salts of zirconium and an organic acid or complex salts mentioned above release ZrO ++ during the process. The product sold under the name of zirconyl acetate is used. The quantity to be used is the same as for the M (OR) 4 derivatives.

Ces catalyseurs sont décrits dans les brevets US 4,332,920 , US 4,230,838 , US 4,331,786 , US 4,252,920 , JP 07145368A , JP 06287547A , et EP 613919 .These catalysts are described in US Pat. US 4,332,920 , US 4,230,838 , US4,331,786 , US 4,252,920 , JP 07145368A , JP 06287547A , and EP 613919 .

La préparation des polyamides est décrite par exemple dans Kunststoff-Handbuch, 3 Technishe Thermoplaste, 4 Polyamide, 1998, Carl Hanser Verlag Münch en.The preparation of the polyamides is described for example in Kunststoff-Handbuch, 3 Technishe Thermoplast, 4 Polyamide, 1998, Carl Hanser Verlag Münch in.

Avantageusement la masse molaire moyenne en poids Mw est comprise entre 10 000 et 30 000 g/mol. Le MFI (abréviation de melt Flow Index ou indice de fluidité à l'état fondu) peut être compris entre 5 et 35 g/10 min (130°C, 2,16 kg)Advantageously, the average molar mass by weight mw is between 10,000 and 30,000 g / mol. MFI (short for Flow Index or Index) melt flow rate) can be between 5 and 35 g / 10 min (130 ° C, 2.16 kg)

S'agissant de la réticulation l'avantage des produits de la présente invention est qu'on les utilise comme des thermoadhésifs conventionnels avec les mêmes machines. Après avoir collé les matériaux, on effectue la réticulation. With regard to crosslinking the advantage of the products of the present invention is that they are used as conventional thermoadhesives with the same machines. After gluing the materials, the crosslinking is carried out.

Ils peuvent être réticulés facilement soit par la chaleur en utilisant des peroxydes comme initiateur soit par rayonnement UV (ou fusion sous UV) en utilisant des initiateurs sensibles aux UV soit par irradiation par des rayons gamma ou bêta.
La source de chaleur peut être un rayonnement infrarouge, la réticulation se fait entre 30 secondes et 5 minutes. Si on réticule sous UV ou sous UV et micro ondes, la réticulation se fait entre 15 et 30 secondes. Quant à la réticulation sous rayonnement gamma ou bêta la réticulation se fait en moins d'une seconde.They can be easily crosslinked either by heat using peroxides as initiator or by UV (or UV melting) using UV-sensitive initiators or by gamma or beta irradiation.
The heat source may be infrared radiation, the crosslinking is between 30 seconds and 5 minutes. If it is crosslinked under UV or UV and microwave, the crosslinking is between 15 and 30 seconds. As for the crosslinking under gamma or beta radiation crosslinking is done in less than one second.

L'activation par la chaleur n'impose pas d'investissements supplémentaires. Le moment et le taux de la réticulation peuvent être contrôlés par le choix du peroxyde avec la température d'activation la mieux adaptée. La réticulation par UV permet de séparer la période d'application du produit à l'état fondu de la période de réticulation, bien que la réticulation soit plus efficace en combinaison avec un réchauffement du produit, comme par les micro-ondes. L'avantage d'utiliser des rayons bêta ou gamma pour réticuler est que c'est presque instantané et qu'aucun initiateur n'est nécessaire.Activation by heat does not require additional investments. The timing and rate of crosslinking can be controlled by the choice of peroxide with the most suitable activation temperature. UV crosslinking makes it possible to separate the application period of the melt product from the crosslinking period, although the crosslinking is more effective in combination with a warming of the product, such as by microwaves. The advantage of using beta or gamma rays to crosslink is that it is almost instantaneous and no initiator is needed.

ExemplesExamples

  • Exemple 1: On condense de l'acide amino-11-undécanoïque du caprolactame et du lauryllactame en présence de diéthylène triamine (DETA), d'acide crotonique et d'héxaméthylène diamine. Example 1 : Amino-11-undecanoic acid is condensed with caprolactam and lauryllactam in the presence of diethylene triamine (DETA), crotonic acid and hexamethylene diamine.
  • Exemple 2: On condense de l'acide amino-11-undécanoïque, du caprolactame, du lauryllactame, de l'hexaméthylène diamine et de l'acide adipique en présence de pentaérythritol et d'acide crotonique. On ajoute ensuite 6g d'un mélange d'acétate de zirconium et de butylate de zirconium sous une pression absolue de 70 mbar-50 mbar et une température de 240°C. On arrête la réaction quand il n'y a plus d'évolution de la viscosité. Example 2: Amino-11-undecanoic acid, caprolactam, lauryllactam, hexamethylenediamine and adipic acid are condensed in the presence of pentaerythritol and crotonic acid. Then 6g of a a mixture of zirconium acetate and zirconium butoxide under an absolute pressure of 70 mbar-50 mbar and a temperature of 240 ° C. Stopping the reaction when there is more evolution of the viscosity.
  • Exemple 3: On condense de l'acide amino-11-undécanoïque, du caprolactame et du lauryllactame en présence de diéthylène triamine (DETA), d'acide undécylénique et d'hexaméthylène diamine. Example 3: Amino-11-undecanoic acid, caprolactam and lauryllactam are condensed in the presence of diethylene triamine (DETA), undecylenic acid and hexamethylenediamine.
  • Exemple 4: On condense du caprolactame, l'acide adipique et d'hexaméthylène diamine et du lauryllactame en présence de diéthylène triamine (DETA) et d'acide undécylénique. Example 4: Caprolactam, adipic acid and hexamethylene diamine and lauryllactam are condensed in the presence of diethylene triamine (DETA) and undecylenic acid.

Les résultats sont présentés dans le tableau 1. Tableau 1 MFI Taux des gels en % (montre une réticulation) Taux des gels en % (montre une réticulation) DMA en g/10min avec 2% peroxide avec 4% benzophénone G' à 160°C en MPa 2,16 kg à 130°C traitement dans malaxeur brabender après UV fusion (lampe D, 350-450 nm, 1100mJ./cm2) après traitement sous les rayons bêta Exemple composition en pourcent des masses des matières premières Luperox® 230, à 155°C Luperox® 231 à 140°C 26 sec 13 sec 50kGy 100kGy 1 6/11/12 = 35/30/35 + 0,2% DETA + 1,6% acide crotonique + 1,14% HMDA 19 78,8% 80,4% 83,90% 32,80% 0,18 0,27 2 6/6.6/11/12 = 30/15/10/45 +1,37% Pentaerytrhitol + 3,46 % acide crotonique 21,4 79,8% 78,2% 86,40% 37,20% 0,018 0,09 3 6/11/12 = 35/30/35 + 0,2% DETA + 3,62% acide undécylénique + 1,14% HMDA 11 - - - 67,6% 0,64 1,12 4 6/6.6/12 =40/25/35 + 0,2% DETA + 3,62% acide undécylénique + 1,14% HMDA 8,8 - - 46,3% 0,75 1,05 Luperox® 230 désigne n-butyl-4,4-di(tert-butylperoxy)valerate CAS N° 995-33-5
Luperox® 231 désigne 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane CAS N° 6731-36-8 DMA désigne analyse mécanique dynamique. The results are shown in Table 1. Table 1 MFI Gels rate in% (shows crosslinking) Gels rate in% (shows crosslinking) DMA in g / 10min with 2% peroxide with 4% benzophenone G 'at 160 ° C in MPa 2.16 kg at 130 ° C treatment in brabender mixer after UV fusion (D lamp, 350-450 nm, 1100 mJ./cm 2 ) after treatment under the beta rays Example composition in percent of the masses of the raw materials Luperox® 230 at 155 ° C Luperox® 231 at 140 ° C 26 sec 13 sec 50 kGy 100kGy 1 6/11/12 = 35/30/35 + 0.2% DETA + 1.6% Crotonic acid + 1.14% HMDA 19 78.8% 80.4% 83.90% 32.80% 0.18 0.27 2 6 / 6.6 / 11/12 = 30/15/10/45 + 1.37% Pentaerytrhitol + 3.46% Crotonic acid 21.4 79.8% 78.2% 86.40% 37.20% 0,018 0.09 3 6/11/12 = 35/30/35 + 0.2% DETA + 3.62% undecylenic acid + 1.14% HMDA 11 - - - 67.6% 0.64 1.12 4 6 / 6.6 / 12 = 40/25/35 + 0.2% DETA + 3.62% undecylenic acid + 1.14% HMDA 8.8 - - 46.3% 0.75 1.05 Luperox® 230 refers to n-butyl-4,4-di (tert-butylperoxy) valerate CAS No. 995-33-5
Luperox® 231 denotes 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane CAS No. 6731-36-8 DMA denotes dynamic mechanical analysis.

Claims (8)

  1. Branched polyamides with unsaturated ends, consisting of:
    • at least one unit originating from a multifunctional monomer (A) chosen from diethylenetriamine, pentaerythritol, mellitic acid and 2,2-dimethylolpropionic acid,
    • at least chains resulting from the condensation, in the presence of at least one unsaturated monoacid used as chain limiter,
    - either of at least two alpha, omega-aminocarboxylic acids not having the same number of carbon atoms,
    - or of at least two lactams not having the same number of carbon atoms,
    - or of at least one lactam, at least one dicarboxylic acid and at least one diamine,
    - or of a lactam and/or of an alpha, omega-aminocarboxylic acid not having the same number of carbon atoms,
    - or of a diamine and of a diacid,
    - or of at least one diamine, of at least one dicarboxylic acid and of at least one alpha, omega-aminocarboxylic acid,
    the proportion of (A) being less than 9% by weight of all of (A) and the above monomers.
  2. Polyamides according to Claim 1, wherein the copolyamide chains comprise at least caprolactam and lauryllactam.
  3. Polyamides according to Claim 1, wherein the copolyamide chains comprise at least caprolactam, hexamethylenediamine and adipic acid.
  4. Polyamides according to any one of the preceding claims, wherein the unsaturated monoacid is crotonic acid or undecylenic acid.
  5. Process for the production of polyamides according to any one of the preceding claims, wherein condensation is carried out, in the presence of an unsaturated monoacid as chain limiter, of at least one multifunctional monomer (A) chosen from diethylenetriamine, pentaerythritol, mellitic acid and 2,2-dimethylolpropionic acid, with
    - either at least two alpha, omega-aminocarboxylic acids not having the same number of carbons,
    - or at least two lactams not having the same number of carbon atoms,
    - or at least one lactam, at least one dicarboxylic acid and at least one diamine,
    - or a lactam and/or an alpha, omega-aminocarboxylic acid not having the same number of carbons,
    - or a diamine and a diacid,
    - or at least one diamine, at least one dicarboxylic acid and at least one alpha, omega-aminocarboxylic acid,
    the multifunctional monomer (A) possibly being present during the condensation of the monomers of the polyamide chains, or added subsequently and a catalyst possibly being added,
    the proportion of (A) being less than 9% by weight of all of (A) and the above monomers.
  6. Hot-melt adhesives comprising the branched polyamides with unsaturated ends according to any one of Claims 1 to 4.
  7. Use, as hot-melt adhesives, of the branched polyamides with unsaturated ends according to any one of Claims 1 to 4.
  8. Use of the branched polyamides with unsaturated ends according to any one of Claims 1 to 4, for sheathing electrical cables.
EP05290820.9A 2004-04-26 2005-04-14 Hot melt compounds made from copolyamides and crosslinkable copolyamide-block-polyethers Active EP1591468B1 (en)

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EP1591468B1 (en) * 2004-04-26 2016-10-19 Arkema France Hot melt compounds made from copolyamides and crosslinkable copolyamide-block-polyethers
CN103249761B (en) * 2010-12-03 2016-08-10 巴斯夫欧洲公司 The method of crosslinked polyamide
FR2974095B1 (en) * 2011-04-13 2014-08-22 Rhodia Operations STABILIZED POLYAMIDE
WO2013004531A1 (en) * 2011-07-01 2013-01-10 Dsm Ip Assets B.V. Branched polyamide with different blocks
CN104558588B (en) * 2013-10-22 2017-09-29 中国石油化工股份有限公司 A kind of nylon polymer and preparation method thereof
FR3026108B1 (en) * 2014-09-23 2018-07-13 Arkema France COMPOSITION FOR THERMOPLASTIC ADHESIVE, THERMOPLASTIC ADHESIVE, METHODS OF MAKING THE SAME, AND USES THEREOF
FR3073774B1 (en) 2017-11-22 2019-11-15 Hexcel Reinforcements REINFORCING MATERIAL COMPRISING A POROUS LAYER OF A PARTIALLY RETICULATED THERMOPLASTIC POLYMER AND RELATED METHODS
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